JPH01123852A - Production of rubber-modified thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the above resin of excellent dispersibility in good efficiency at a small heat consumption by using a simple inexpensive apparatus, by feeding a specified graft rubber polymer latex, a water-soluble chemical, an organic chemical, etc. to a continuous kneader through respective inlets, feeding the separated organic phase to an extruder and processing it. CONSTITUTION:A graft rubber polymer latex prepared by the emulsion graft polymerization of a vinyl monomer with a rubber latex is fed to a continuous kneader through an inlet II; at most 10wt.%, based on the graft rubber polymer, water-soluble chemical which coagulates the latex is fed to it through an inlet III; 10-600wt.%, based on the graft rubber polymer etc., organic chemical of a water solubility <=5wt.% (at the barrel temperature at a water exit VI) is fed from an inlet IV to the coagulated latex mixture obtained during the course to an inlet IV distant from the inlets II and III by a distance L1 which is one to five times as large as the screw diameter; the water phase separated by kneading during the course to a distance L2 of 4D-20D is discharged through an exit VI; the graft rubber polymer mixture is discharged through an organic phase discharge exit IX and is fed to an extruder through an inlet XI to obtain the above resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention produces a rubber-modified thermoplastic resin by mixing a grafted rubber polymer obtained by graft polymerizing a vinyl monomer with a thermoplastic resin. Regarding the method in more detail, the graft rubber is produced by mixing the precipitate of the graft rubber polymer Latinx and the thermoplastic resin in the presence of a specific organic agent using a relatively inexpensive continuous kneader and extruder. The present invention relates to a method for efficiently producing a rubber-modified thermoplastic resin with excellent particle dispersibility using simple and inexpensive equipment and using a small amount of heat.

[Conventional technology]

Most of the rubber-modified thermoplastic resins represented by ABS resins are resins obtained by mixing and kneading a polymer obtained by graft polymerizing a vinyl monomer to rubber latex and a thermoplastic resin. . The manufacturing process generally includes an emulsion graft polymerization process, a coagulation process, a dehydration drying process, a blending process, and a melt extrusion process.

In the emulsion graft polymerization process, acrylic monomers, vinyl cyanide monomers, aromatic vinyl monomers, etc. are added to diene rubber latex, vinyl rubber latex, natural rubber latex, silicone rubber latex, etc. This is a process of emulsion graft polymerization to form a graft polymer latex. In the coagulation process, a coagulant such as a polyvalent salt or acid is added to the graft polymer latex to break the emulsified state and form polymer 1[
This is the process of analyzing and turning it into powder.

In the dehydration and drying process, the aqueous phase is separated from the mixture of powdered polymer and water by means such as centrifugal dehydration, and then dried by means such as fluidized drying. This is the process of obtaining The blending process is a process of blending the dry powder with other thermoplastic resins and additives such as stabilizers, lubricants, and plasticizers, and the melt extrusion process involves melting and kneading the blended raw materials using a device such as a screw extruder. This process involves extruding it into strands and shaping it into pellets.

The first problem in terms of production and quality of the rubber-modified thermoplastic resin produced through each of the above steps is that the amount of heat used is large. This is due to the use of a large amount of hot air in the drying process. The second problem is that because the graft rubber particles are completely fixed in the coagulation process, it takes a lot of power to disperse the fixed graft rubber particles into the thermoplastic resin during the melting and cross-crossing operation after blending. It is necessary to. In the worst case, it becomes industrially impossible to uniformly disperse the graft rubber particles in the thermoplastic resin.

Several proposals are known in order to improve the traditional manufacturing methods that involve such intermediates that lead to a decline in industrial competitiveness when producing rubber-modified thermoplastic resins, some of which include It is being carried out on a regular basis. One of them is to reduce the heat usage t' in the drying process, which utilizes a screw type extruder having a dehydration function, which is generally called a dehydration extruder. This method includes a first method in which the wet graft rubber powder after coagulation and dehydration is blended with other thermoplastic resins and additives, or the wet graft rubber powder is fed alone to a dehydrating extruder; The method is broadly divided into a second method in which the Latinx and coagulant are supplied to the dehydration extruder together with other thermoplastic resins and additives as the case may be.

Since this method does not require a drying process that uses a large amount of hot air, it is highly effective in terms of reducing the amount of heat used, but it is on the same level as conventional techniques in terms of uniformly dispersing the Hegelaft rubber particles in the thermoplastic resin. . That is, in the first method, the graft rubber particles are processed in a completely fixed state, so that the method is equivalent to the conventional technology from the viewpoint of particle dispersion. In the second method, the latex and coagulant are first mixed in the processing equipment, and then heated to 100°C.
Dehydration is carried out at a temperature range of a certain degree or less, at which point the grafted rubber particles are usually stuck together. Then, as the temperature rises, the thermoplastic resin and the thermoplastic resin melt together and are subjected to cross-wire operation, so the first method differs only in the state of the raw material supplied, and from the viewpoint of particle dispersion, it is different from the old technology. It is not beyond the scope of.

Another method is to mix the grafted rubber polymer latex, coagulant, and monomer into a two-phase mixture consisting of an organic phase and an aqueous phase, and then separate the aqueous phase and remove the monomers contained in the organic phase. A method of polymerizing monomers and a method of polymerizing monomers in the two-phase mixture without separating the aqueous phase, then separating the aqueous phase and drying the polymer have been proposed. Since these methods do not involve a process in which the graft rubber particles completely adhere to each other, they are very unique in terms of particle dispersion compared to the aforementioned method using a dehydrating extruder.

However, in the former method, it is necessary to polymerize a highly viscous mixture consisting of a cake-like graft polymer and a monomer without causing a runaway reaction, which is difficult in terms of equipment and operation. It is hard to say that this is a method that has been completely immersed. Moreover, in rubber-modified thermoplastic resins, because the content of the rubber component has a great influence on the basic physical properties of the resin, polymerization is carried out at a low polymerization rate with large fluctuations, as is done in ordinary bulk polymerization methods. It is not possible to use a method in which the remaining monomers are devolatilized after completion of the reaction, and the reaction must proceed until a high polymerization rate with small fluctuations in the polymerization rate is obtained. It has a high viscosity and high temperature compared to that of the conventional method, making it extremely difficult to handle. In addition, the latter method involves polymerizing monomers by suspension polymerization, and while the viscosity of the system is low and the heat of reaction can be easily removed, there remains the problem that dehydration and drying steps are required. has been done.

[Problems to be Solved by the Invention Many proposals have been made regarding the production method of co-rubber-modified thermoplastic resins. At present, a high-quality and competitive method for producing the resin that simultaneously solves the problems of dispersion and reduction of the amount of heat used has not yet been completed.

The present inventors took issue with this current situation and proposed a method for manufacturing a rubber-modified thermoplastic resin that enables a similar dispersion of grafted rubber particles in a thermoplastic resin and is energy-saving. Special application 1986-110
No. 989, t'f! f Japanese Patent Application No. 60-295369, Japanese Patent Application No. 1982-295952, Japanese Patent Application No. 1983-295955, Japanese Patent Application No. 60-295569, Japanese Patent Application No. 1987-2955
No. 70, Japanese Patent Application No. 166571/1983 and Japanese Patent Application No. 1983
-175508 and other methods were proposed to solve the problems of conventional methods. As a result of further studies, the present inventors have found a method for producing rubber-modified thermoplastic resin with high productivity using simple and inexpensive equipment without losing the advantages of the above proposal, and have completed the present invention. It was.

[Ninth way to solve the problem]

That is, the method for producing a rubber-modified thermoplastic resin of the present invention is as follows:
Graft rubber polymer (1) obtained by emulsion graft polymerization of vinyl monomer to rubber latex, thermoplastic resin (3)
, and optionally thermoplastic resin (2) using a continuous kneader and an extruder, the following supply ports (II), (L head, (6) and (capital)) , a drainage port, and a discharge port, (II): latex (A) of graft rubber polymer (1);
) supply port, (110: supply port for a water-soluble drug (c) capable of coagulating latex (A)′, which is 10% by weight or less based on the graft rubber polymer (1)) (IV): supply port (■) and supply port @) of the following organic drug, which is located on the discharge side by a distance (L1) from 1 to 5 times the screw diameter (D), and from the organic drug): Graft rubber Polymers and thermoplastic resins (2
), and has the ability to dissolve 10 to 600% by weight of the thermoplastic resin (2), and has a solubility in water that is higher than that of the barrel of the drain port (6) described below. ) 5M amount%
From a mixture of the following organic chemicals (■: located on the discharge side from the supply port (VI) to the supply port by a distance (L2) of 4 times or more and 20 times or less of the screw diameter (D)) Drain port for discharging the separated aqueous phase, (ω: discharge port for the organic phase containing the graft rubber polymer, and if desired, if thermoplastic resin (2) is used, the following (1), (V), The thermoplastic resin (2) supply port has one supply port of the thermoplastic resin (2) among the supply ports, and the thermoplastic resin (2) supply port is located on the drive side from the supply port (II) and the supply port section). , (V): Supply port of the thermoplastic resin (2) located on the discharge side from the supply port ([I) and supply port @), ■: If there is a supply hole ■, the screw diameter CD is from the stile, the supply port - ) is located on the drive side by a distance (L3) that is at least 2 times and 10 times as long as the thermoplastic resin (2
) Supply port ζ Furthermore, if desired, there is a continuous kneading machine having a supply port for the thermoplastic resin (3) shown below. ) is located on the drive side, and the supply port for thermoplastic resin (3) is located on the drive side, and the following (1) 1. (Xll1) and (punishment) have a supply port 1 pentro and a discharge port, (X): a supply port for supplying the organic phase mixture containing the graft rubber polymer (1) discharged from the continuous kneader; ( Xfl1): Vent hole at 1 to 4 locations to vaporize and remove the organic agent (B) and the remaining aqueous phase that is not discharged through the drain port (4); Discharge port 1 Furthermore, if the thermoplastic resin (2) is used as desired, the following supply port (XI) is provided.
The supply port (Xn) is located on the drive side by a distance (L3) that is between twice and 10 times the screw diameter
If you do not have 'e, distance 11i from Ventro (xI)
The thermoplastic resin (2) supply port is located on the driving side by 1L5, and if the thermoplastic resin (3) is used as desired, the following supply ports (Xl1) and (XIV) are provided.
I[): Supply port for the thermo-OT plastic resin (3) located on the drive side by a distance (-4) from 1 to 10 times the screw diameter of Pentro (Xll1), (XIl/): Pentro ( If the thermoplastic resin (3) supply port is located on the discharge side from
: Supply port (XIV)! ! Distance (L4) Vent holes located on the discharge side, with one or more and two or less locations for removing volatile components contained in the rubber-modified thermoplastic resin product, and a supply port for the thermoplastic resin (3). As for the supply port (X) in the continuous kneading machine,
), the latex α) is supplied from the supply port (II) of the continuous kneading machine, the water-soluble drug (0) e is supplied from the supply port ('ff1), and the latex ( Distance L1 between A) and water-soluble drug (C)'
The organic drug @) is supplied from the supply port (IV) to the mixture containing the coagulated latex (A) obtained by mixing in the interval of L2, and the latex (A) is mixed in the interval of distance L2. ' is separated into a mixture containing the graft rubber polymer (111, -) and an aqueous phase, and the aqueous phase is discharged from the continuous kneading machine through the drain port (4), and then the mixture containing the graft rubber polymer (1) is separated. is discharged from the discharge port vessel, and then the discharged material is supplied to the extruder from the supply port (3), and then the organic phase mixture containing the graft rubber polymer (1) is heated and ventilated (XOI). of organic drugs) and outlet (6)
The moisture that has not been discharged is removed by degassing, and if desired, the thermoplastic resin (2) is added to the feed port (1) of the continuous kneading machine.
Or supply from one of the supply port ('V) or the supply port width or the supply port (XI) of the extruder, and distance x from the mixture contained in 1 (of graft rubber polymer (1) and organic drug)
Mixing in section J3, and supplying the thermoplastic resin (3) from at least one supply port of the supply port width of the continuous kneading machine, the supply port (Xn) or the supply port (XIV) of the extruder, Mixture containing graft rubber polymer (1) and distance L
4, and optionally ventro (X'v)
It is characterized by degassing volatile components.

The rubber latex used in the present invention is not limited in any way as long as it is a latex of a polymer that has rubber elasticity within the operating temperature range of the target rubber-modified thermoplastic resin, such as polybutadiene, polyimprint, etc. latex of diene-based rubber such as N, 8ER; latex of olefin-based rubber such as ethylene-propylene rubber, ethylene-vinyl acetate rubber; latex of acrylic rubber such as polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polybutyl acrylate, etc. ; Examples include latex of silicone rubber such as polydimethylsiloxane. These rubber latexes may be used alone or in combination of two or more.

It is extremely difficult to uniformly disperse the rubber particles contained in such rubber latex into a thermoplastic resin using conventional methods, and even if it is possible to do so with a temporary adhesive, the phase between the rubber and the thermoplastic resin is extremely difficult. Due to poor solubility, etc., satisfactory physical properties could not be achieved. Therefore, graft polymerization is carried out as a means to improve compatibility, enable uniform dispersion of rubber particles, and develop unique physical properties. The monomers used in this graft polymerization are: Vinyl monomers are used because the polymerization method is emulsion radical polymerization, and they are optimal from the viewpoint of compatibility with the thermoplastic resin to be blended, adhesiveness, etc. Generally, one is selected. This situation does not change in the present invention. Therefore, the vinyl monomers to be graft-polymerized to the rubber used in the present invention include conventionally used vinyl cyanide monomers such as acrylonitrile and methacrylate, and aromatic vinyl monomers such as styrene and alpha-methylstyrene. monomers, methacrylates such as methyl methacrylate and phenyl methacrylate, 10genated vinyl monomers such as methyl chloroacrylate and 2-chloroethyl methacrylate, and other radically polymerizable monomers.

As the thermoplastic resin (2) used in the present invention, any resin soluble in the organic agent ω to be described later can be used. Acrylonitrile-styrene copolymer, acrylonitrile-α-
Methylstyrene copolymer, acrylonitrile-α-methylstyrene-N-phenylmanoid copolymer, polystyrene, polymethyl methacrylate, polyvinyl chloride,
Typical examples include polycarbonate, polysulfone, and polyethylene terephthalate.

On the other hand, thermoplastic resin (3) ta, , thermoplastic resin (
Although it does not need to be soluble in the organic agent (B) like 2), specific examples include resins similar to those exemplified in the thermoplastic resin (2) above. The thermoplastic resin (2) and the thermoplastic resin (3) may be the same or different.

The organic agent φ) that can be used in the present invention must have a solubility in water of 5 weight or less, preferably 2 weight or less at the drain outlet of the continuous kneading machine (VD barrel temperature @), and It is an organic agent that can dissolve the plastic resin (2). 10 to 600% of the total amount of the graft rubber polymer (1) and thermoplastic resin (2) to this organic agent
The weight ratio is preferably 20 to 200 weight ratio.

In this case, if the solubility of the organic drug () in water is 5% by weight or more at the temperature @), the aqueous phase discharged from the drain port (6) will become cloudy. That is, the organic drug) and polymer components soluble therein are mixed into the aqueous phase, and a large amount of equipment is required to treat the discharged aqueous phase. Furthermore, the usage efficiency of the added organic agent (B) decreases, and the yield of the polymer product also decreases, which is not preferable.

On the other hand, if the amount of the organic agent (1B) used is less than 10% by weight with respect to the total amount of the graft rubber polymer (1) and the thermoplastic resin (2) contained in the latex (A), the present invention is effective. If the organic drug CB) is used in an amount exceeding 600% by weight, a large amount of heat will be required to separate the organic drug, which is undesirable from an industrial standpoint.

Specific examples of organic agents that can be used in the present invention include petroleum ether, benzene, toluene, xylene, ethylbenzene, diethylbenzene, p-cymene, aromatic hydrocarbons such as tetralin, methylene chloride, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, tricrene, chlorobenzene, and epichlorohydrin; ketones such as methyl-n-propyl ketone and acetophenone; ether compounds such as n-propyl acetate and n-butyl acetate; Examples include, but are not limited to, aliphatic hydrocarbons such as heptane, non-polymerizable organic agents such as 1-nitropropane, and polymerizable organic agents such as styrene, methyl methacrylate, and α-methylstyrene. As long as they satisfy the above conditions, they can be used alone or in combination of two or more.

The water-soluble drug (c) rx with coagulation ability that can be used in the present invention may be any water-soluble substance that has the ability to coagulate the latex h>' used, and the quality of the resin to be produced. From the viewpoint of not causing deterioration, the proportion by weight of the graft rubber polymer (1) is 10 or less,
It is preferably used in a range of 5% or less, more preferably 3% or less. In addition, water-soluble drugs generally contain (l
Use L2 weight i% or more. Specific examples of water-soluble drugs (C) include aluminum sulfate, aluminum chloride,
Examples include polyvalent salts such as aluminum nitrate, magnesium sulfate, calcium chloride, and calcium nitrate, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and propionic acid.

The thermoplastic resin (2) is at least a distance L between the supply port (IV) of the continuous kneader and the supply port (Xl1) t of the extruder.
By mixing and kneading with the graft rubber polymer (1) in the presence of a specific amount of organic agent @) in three or more sections, the graft rubber polymer particles in the graft rubber polymer (1) are converted into a thermoplastic resin. (2) It has the function of uniformly dispersing the graft rubber polymer particles in the polymer and preventing the graft rubber polymer particles from re-agglomerating and becoming poorly dispersed in subsequent steps. In order to exhibit such "uniform dispersion function" or "reaggregation prevention function", the amount of thermoplastic resin (2) must be higher than that of graft rubber polymer (1) containing a large amount of "tree polymer" described below. Except when using
The content of the thermoplastic resin (2) and the graft rubber polymer (
1) The presence of a certain amount or more of the organic agent when the two are mixed and kneaded, and the kneading is performed in a distance L3 that is at least twice the screw diameter in order to obtain a uniform dispersion state. is important. .

The feeding position of the thermoplastic resin (2) is the graft rubber polymer (
It is desirable to decide by taking into consideration the affinity between 1) and the thermoplastic resin (2) and the organic agent) and the volumetric efficiency of the device. That is, the graft rubber polymer (1) and the organic drug (to)
If the affinity is too high, even if the entire thermoplastic resin (2) is supplied from the supply port n of the continuous kneader or the supply port (XI) of the extruder, the dissolution and mixing effect of the organic agent may be insufficient. υ, thermoplastic resin (2) and graft rubber polymer (1
) may not be sufficiently mixed and dispersed, and the graft rubber particles of the graft rubber polymer (1) may not be uniformly dispersed in the thermoplastic resin (2). In such a case, connect the feed port (V) of the continuous kneader (13 to 9) to the multi-thermoplastic resin (2).
It is desirable to supply the latex material (latex body) and the thermoplastic resin (2) to perform the crosstalk in a state where they coexist. Whether to supply from the supply port (1) or the supply port (V) may be determined depending on the raw materials and equipment used. Generally, the supply port (1) supplies the thermoplastic resin (2) to the screw that is not filled with anything, so the thermoplastic resin (2)
is smoothly taken into the extruder, allowing stable operation. On the other hand, from the supply port (V), thermoplastic resin (2)
If it is possible to supply the stile, the supply port < y) is the supply port (II)
By installing the continuous kneading machine between the supply port @) and the distance L1 between the supply port (goods), the size of the continuous kneading machine can be made smaller than when the supply port (1) is provided. Furthermore, even if the multi-thermoplastic resin (2) is fed through the feed port M6 of the continuous kneading machine and the feed port (XI) of the extruder, the graft rubber particles of the graft rubber polymer (1) are not mixed with the thermoplastic resin (2). If the thermoplastic resin (2) is to be uniformly dispersed in the water phase, it is better to supply the thermoplastic resin (2) from the supply port (to) or the supply port (XI') because the aqueous phase discharged from the drain port (VD) and the thermoplastic resin ( 2
) is preferable because it does not coexist and the volumetric efficiency of the device is improved.

The width of the feed port of the continuous kneader or the feed port 00 of the extruder may be determined depending on the raw materials and equipment used. In general, if the feed is carried out through the feed port, mixing can be carried out using a continuous kneader, which is cheaper than an extruder, and the extruder can be made smaller.

The graft rubber polymer (
Although it varies depending on the type of 1) and the desired physical properties of the final rubber-modified thermoplastic resin product, it is usually appropriate to use less than the thermoplastic resin contained in the rubber-modified thermoplastic resin product.

When the entire amount of thermoplastic resin required to make a rubber-modified thermoplastic resin product is added as thermoplastic resin (2), a large amount is added to uniformly disperse the grafted rubber polymer particles in thermoplastic resin (2). This results in the disadvantage that the amount of organic agent to be removed in the ventro (Xln) and ventro (x'v) of the extruder, which requires organic agent, increases, and therefore the thermal energy required for removal increases. Furthermore, since the amount of mixing and kneading of the graft rubber polymer (11) which must be mixed and kneaded in order to uniformly disperse the graft rubber particles increases, there is also the disadvantage that the mixing energy increases and the productivity of the mixing device decreases. .

In order to avoid such disadvantages in the present invention, the thermoplastic resin necessary for producing the rubber-modified thermoplastic resin product is thermally combined with the thermoplastic resin (2) soluble in the organic agent (D). Mix the plastic resin (3) separately.

On the other hand, if a large amount of vinyl monomer is used during the polymerization of the graft rubber polymer (1), a polymer C in which the vinyl monomer is polymerized alone without being graft-polymerized to the rubber is called a "free polymer". ) is contained in a large amount in the graft polymer, and this "free polymer" is the above-mentioned thermoplastic resin (2
) instead, it may exhibit a "reaggregation prevention function".

Therefore, in such a case, the rubber-modified thermoplastic resin is not supplied at all through the supply port (1) or the supply port (V) or the supply port (Vlt or supply port diagram). Assuming that the total amount of thermoplastic resin necessary to obtain the product is thermoplastic resin (3), the feed port width and/or width of the continuous kneader is determined by the feed port (Xn) and/or feed port (XI) of the extruder.
V).

The thermoplastic resin (3) is supplied through the supply port (xN) and/or the supply port width and/or width (Xl1).

Among these, the thermoplastic resin (3) added at the supply port - and the supply port (XI[') has the function of reducing coloring of the mixture in the next step, so it is necessary to mix and knead it thoroughly. do not have. That is, the mixture is usually heated in a ventilator (Xl[['), and the organic agent(s) and remaining water in the mixture are evaporated and removed, optionally under reduced pressure. When the organic agent (B) is removed from the mixture, the dissolution or plasticizing effect of the organic agent (B) disappears, and the mixture now contains the grafted rubber polymer (1), the thermoplastic resin (2), and the thermoplastic resin. Polymer (5), which is a mixture of (3), begins to exhibit dissolution/flow behavior.

In order to process the mixtures smoothly in the extruder, it is necessary to keep the temperature of these mixtures above the flow initiation temperature. Furthermore, the evaporation of the residual moisture (in the organic agent) takes place in a relatively short period of time, and heating due to external heat supply and shear heat cannot be expected. Considering that most of the latent heat of vaporization of the organic drug) and residual water must be covered by the sensible heat generated by the temperature reduction of the mixture,
It becomes necessary to heat the mixture to a temperature considerably higher than its flow initiation temperature.

However, when exposed to such high temperatures, the rubber components contained in the graft rubber polymer (1), particularly diene rubbers such as polybutadiene, deteriorate due to heat and turn yellow. This yellowing phenomenon is particularly noticeable when the amount of rubber component in the mixture increases, and especially when the amount of diene rubber component is 40%
% in the above mixtures. In other words, even if the product has the same amount of rubber component, the above mixture with a large amount of rubber component is degassed and then the supply port (I
Add the thermoplastic resin (3) in XIv) and carefully adjust the supply port width to the colored state of the product.
) is mixed, and the coloring condition is worse than that of a product that is deaerated with a reduced amount of rubber components contained in the mixture. Therefore, in order to reduce the coloring of the rubber-modified thermoplastic resin product, it is preferable to add at least a portion of the thermoplastic resin (3) to the supply port 1I or the supply port (XII).

Which of the supply port (1) or the supply port (Xn) should be used may be determined depending on the raw materials and equipment used. Generally, when the material is supplied through the supply port, a continuous kneader, which is cheaper than an extruder, is used to supply the material, so the extruder can be made smaller.

On the other hand, if a large amount of organic agent remains in a rubber-modified thermoplastic resin product, its plasticizing effect will lower the heat distortion temperature, hardness, etc., and furthermore, bubbles of organic agent vapor may be mixed into the molded product during molding. Since the toxicity of organic drugs is a problem in food applications and the like, it is desirable that the residual amount of organic drugs in rubber-modified thermoplastic resin products be as small as possible. Normally, it is necessary to make it less than 1 weight factor, more preferably less than 15 weight factor. This “residual organic drug concentration reduction function”
It is desirable to add the thermoplastic resin (3) to the feed port (XIv). The reason for this is believed to be the evaporation rate characteristics of the organic drug from the mixture of polymer and drug. That is, by raising the temperature of the mixture above the boiling point of the organic drug in a region where the concentration of the organic drug in the mixture is high, the organic drug in the mixture can be removed by degassing relatively quickly. However, when the organic drug concentration in the mixture becomes low, reaching less than 5 to 1 weight percent (however, this value varies depending on the combination of polymer and organic drug), the evaporation rate of the organic drug decreases significantly. , it becomes difficult to degas the organic drug from the mixture.

Therefore, after degassing the thermoplastic resin (3) without completely mixing it to lower the organic drug concentration in the mixture to 5 to 1% by weight or less, the thermoplastic resin (3) was added at the supply port (XIV). Therefore, it is advantageous to dilute the organic agent in the mixture by adding it.

Therefore, the entire jlt1r of the thermoplastic resin (3), the width of the supply port, the supply port (Xl1), and the supply port (XI'/) may be mixed at any one of the locations, but the above-mentioned "coloring reduction function" In order to harmonize the "residual organic drug concentration reduction function", the thermoplastic resin (3) is placed between the supply port and the supply port (
It is desirable to distribute and mix at the supply port (X■) and the supply port (XIV).

The reason why the graft rubber particles can be uniformly dispersed in the thermoplastic resin by the method of the present invention is that the graft rubber particles are always in a dispersed state or in a soft agglomerated state without going through the conventional process of completely fixing them. This is considered to be the process leading to the final product. Furthermore, in the method of the present invention, conventionally,
There is no need to use a dryer that generates a large amount of heat loss, and the desired rubber-modified thermoplastic resin can be produced using a continuous kneading machine and extruder. A huge contribution will be made.

[Embodiments of the invention]

The method of the present invention will be specifically explained below using Examples and Reference Examples. Note that all parts in the Examples and Reference columns are based on weight.

(Polymerization of raw material polymer) Polymerization of graft rubber polymer (1): Q. Graft polymerize acrylonitrile and styrene to polybutadiene latex having an average particle size of 36 μm according to the recipe in Table 1 to obtain a graft rubber polymer. Union (i
) latex ゛9.

Table 1 Polybutadiene latex 114.
3 parts (40 parts based on solid content of polybutadiene) Acrylonitrile 15 Styrene
451 Sodium Laurate
a, 5 Sodium hydroxide
α01N Longalit [L2
1 Ferrous sulfate CLo02〃F
JDTA-2 sodium salt Q,
1/Iter to butyl hydroperoxide
Q, 3 Lauryl mercaptan 13N deionized water 125N polymerization temperature
70℃ polymerization time
240 minutes Polymerization of grafted rubber polymer (11) A latex of grafted rubber polymer (ii) was prepared using the same chemicals as those for grafted rubber polymer (i) and according to the formulation shown in Table 2.

Table 2 Polybutadiene latex 22 & 6 parts (polybutadiene solid content equivalent: 80 parts) Acrylonitrile
5 Styrene
15 I Sodium Laurate
α4 Sodium hydroxide a, oi
p Rongarit α15 #
Ferrous sulfate α0011EDTA
-2 sodium salt 0.05 1
1, er is butyl peroxide a,
1〃Lauryl mercaptan [11N deionized water 50 tt Polymerization temperature
70℃ polymerization time
Polymerization of grafted rubber polymer 611) for 280 minutes Using the same chemicals as for grafted rubber polymer (i), the third
A latex of graft comb polymer (iii) was prepared by graft polymerization according to the recipe in the table.〇Table 3 Polybutadiene latex 85.7 parts (
Polybutadiene solid content equivalent: 30 parts) Acrylonitrile 17.5N styrene
52.5 #Sodium Laurate
06N sodium hydroxide (L
Ol 10 Ngaritz Cl3
#Ferrous sulfate 1002〃1
1CDTA-disodium salt α1
2 ter is butyl hydroperoxide
α35 N lauryl mercaptan 1llL
55# Deionized water 146〃Polymerization@
degree 70℃ polymerization time
240 minutes grafted rubber polymer (V
): Polymerization of methyl methacrylate and methyl acrylate into 13PR rubber latex having an average particle size of 114 μm.
Graft polymerization was carried out according to the recipe shown in the table to obtain a latex of graft rubber polymer 4v).

Table 4 SBR rubber latex 100 parts (EI
BR rubber solid content equivalent: 50 parts) Methyl methacrylate 45 Methyl acrylate 5 Potassium rosinate
1N Rongalito
(121 ferrous sulfate 1lLoo
511! iDT Mu-disodium salt
α1N Kiyumen Hydroperoxide
α4 #Octylmercaptan (1
2# Deionized water 15o Polymerization temperature 65℃ Polymerization time
240 minutes Polymerization of acrylonitrile-styrene copolymer: thermoplastic resin (
Acrylonitrile-styrene copolymers used as 2) and (3) were produced.

Table 5 Acrylonitrile 25 parts Styrene 75 Azobisin butyronide substitute Cl5 N lauryl mercaptan
I15 If polyvinyl alcohol (degree of polymerization 9
00) [LOl N Sodium Sulfate
(L5 #Water
250 〃Polymerization temperature
75℃ polymerization time
After 240 minutes of polymerization, the obtained acrylonitrile-styrene copolymer suspension was centrifugally dehydrated and dried at 80°C to obtain a powder of the polymer.

Polymerization of polymethyl methacrylate: Thermoplastic resins (2) and (3) according to the formulation in Table 6
Polymethyl methacrylate was produced to be used as

Table 6 Methyl methacrylate 100 parts Azobisisobutyronitrile α3 Lauryl mercaptan α5 Polyvinyl alcohol (degree of polymerization 900) α07 1 Sodium sulfate
(L25 #Water
200 1 Polymerization temperature
80℃ polymerization time
After 180 minutes of polymerization, the resulting suspension of polymethyl methacrylate was centrifugally dehydrated and dried at 80°C to obtain a core polymer powder.

Examples 1-7 Diameter 30m as shown in Figure 3 and Table 7.

A co-rotating twin-screw kneader with an effective screw part length of 610 mm is equipped with a drain port (H = 3 w,
W = 10 m) 1 and with a diameter of 50 m5 as shown in Figure 4 and Table 7. A bent boat shown in Figs. 9 and 10 was attached to a co-rotating twin-screw extruder with an effective screw part length of 725 mm, and latex of grafted rubber polymer of type and base shown in Table 8 was prepared at latitude r: 1. .5
An attempt was made to produce a rubber-modified thermoplastic resin pellet by supplying an aqueous solution of 1% sulfuric acid, an organic drug, and an acrylonitrile-styrene copolymer as the thermoplastic resin (2) and the thermoplastic resin (3). In the thermoplastic resin (3), a molding aid (Aramide HT, trade name, manufactured by Lion Armor Co., Ltd.) having a weight ratio of α15 to the total polymer was dispersed and mixed in advance (f?4).

The temperatures of the continuous kneader and extruder were set as shown in Table 7, the screw rotation speed of the continuous kneader was 40 rpm, and the screw rotation speed of the extruder was 200 rpm. The supplied latex of the graft rubber polymer is mixed with an aqueous sulfuric acid solution with a weight ratio of υ, which is supplied by a plunger type pump from the supply port (@), and is completely coagulated by the time it reaches the supply port (goods). It turned into a creamy substance. The organic agent (toluene or ethylbenzene) shown in Column 5 of Table 8 was supplied in a fixed amount to the creamy substance from the supply port (IV) by a plunger type pump, and was mixed in section L2 to form a cake-like organic phase. The aqueous phase was separated, and the aqueous phase without any cloudiness was discharged from the drain port (4).

The cake-like organic phase is wrapped around the screw and cannot be discharged from the outlet. The organic phase is further compressed and dehydrated by a combination of the screw elements shown in FIGS. 13 to 16 provided between sections L2 and L5 and the kneading disks shown in FIGS. 17 to 18, and the dehydrated water is It returned to the drive side and was discharged from the drain port (VI). Supplying acrylonitrile-styrene copolymer powder in the amount shown in column 7 of Table 8 as a thermoplastic resin (2) to the dehydrated organic phase using a υ belt feeder from the supply port (to),
The rice cake-like organic phase is kneaded by a kneading disk having a shape shown in FIGS. 17 to 18 and provided in section L3, and is discharged from a discharge port having a diameter of 20 cm as shown in FIG. 12.
The mixture was press-fitted into a pipe of w+s+ and length 100 cm, and supplied to the extruder from the extruder supply port (1) shown in FIG.

The supplied cake was heated at the temperature shown in Table 7, and then reduced to the pressure shown in column 10 of Table 8 using a ventilator (xliI) to remove the organic drug in the organic phase and the remaining aqueous phase. Air was removed to obtain a mixture of graft rubber polymer and thermoplastic resin (2). Acrylonitrile-styrene copolymer powder was supplied to the resin mixture from the supply port (Xll/) by a belt type feeder, mixed in section L4, and then heated to the pressure shown in column 10 of Table 8 using a ventilator (XV). Reduce the pressure to
The volatile components remaining in the resin mixture were removed by degassing, and the rubber-modified thermoplastic resin product was discharged in the form of a strand from the discharge port (xVt). This was water-cooled and made into pellets. The obtained pellet was smooth, and no uneven portions called fins were observed. Various test pieces were made by injection molding this and various physical property values were measured, and the results shown in Table 9 were obtained. These values indicate that the rubber-modified thermoplastic resin produced in this example is excellent.

Table 7 Example 8 Shapes shown in Figures 19 to 21 as drain ports (W = '
(15w, H=5m, pickpocket 7) In addition to using the one described in Equation 10), the same continuous kneading machine and extruder as in Example 1 were used, and rubber denaturation heat was applied under the conditions shown in Table 8. Producing plastic resin.

At the drain outlet (■), the separation of the organic phase and aqueous phase was incomplete, and part of the organic phase became particulate matter and was separated into the aqueous phase.
The aqueous phase filtered and drained through the drain outlet slits shown in Figures to Figure 21 contained almost no organic phase.

Practical rows 9 to 10 Using the same continuous kneader and extruder as in Practical row 1, the screw rotation speed of the continuous kneader was 300 r at the temperature shown in Table 10.
pm, extruder screw rotation speed 200 rpm,
A latex of grafted rubber polymer 4v) as shown in Table 11, @ degree Q, 31% aqueous magnesium sulfate solution, chloroform and polymethyl methacrylate were supplied as thermoplastic resins (2) and (3). A rubber-modified thermoplastic resin belene ht was produced in the same manner as in Example 1.

The resulting pellets were smooth and no uneven areas called fins were observed. This was injection molded to create various test pieces, and various physical property values were measured, and the results shown in Table 12 were obtained. These values indicate that the rubber-modified thermoplastic resin produced in this example was affected.

Table 10 Table 12 Example 11 Using the same continuous kneader and extruder as in Example 1, the screw rotation speed of the continuous kneader was 45 Orp at the temperature shown in Table 13.
m, extruder screw rotation speed 250 rpm, 37.5 parts of latex of graft rubber polymer (11), α
50 parts of 3 parts by weight aqueous sulfuric acid solution and 20 parts of dichloromethane were supplied from the supply ports (■), (111), and (IV), respectively. Further, 12.5 parts of acrylonitrile-Rustin copolymer was supplied as the thermoplastic resin (2) from the supply port (4), and polycarbonate resin (Novarenx 7022, trade name, Mitsubishi Chemical Industries, Ltd.) was supplied from the supply port (XN'). Co., Ltd.)
A rubber-modified thermoplastic resin pellet was produced in the same manner as in Example 1 at the temperature shown in Table 13 by adding 75 parts.

This pellet contains 1 cLO weight of butadiene, which is not approved by the drug. Table 14 shows the test results of test pieces obtained by injection molding the pellets.

Tables 13 and 14 (Test methods are the same as in Example 1.) Implementation flIJ12-14 Co-rotating twin screw extrusion with diameter 30fi and screw part length 470mm as shown in Figure 13 and Table 13 5th on machine
- Drain port shown in Figure 6 (II=3 tll, W=
10■), and also attached the penthotra shown in Figures 9 to 10 to a co-rotating twin-screw extruder with a diameter of 30mm and a screw part length of 825mm as shown in Figure 14 and Table 13. Graft rubber polymer latex of the type and amount shown in Table 16, sulfuric acid aqueous solution with a concentration of 0.5% by weight,
A rubber-modified thermoplastic resin pellet was produced in the same manner as in Example 1 by supplying an organic drug and an acrylonitrile-styrene copolymer as a thermoplastic resin (2) and a thermoplastic resin (3). The plastic resin (3) contains a molding aid (Aramide IT) containing Q and 15% by weight based on the total polymer.

(trade name, manufactured by Lion Armor) were dispersed and mixed in advance. ).

The resulting bullet was smooth, and no uneven parts called fish eyes were observed. When various test pieces were made by injection molding and various physical property values were measured, the results shown in Table 17 were obtained. These values indicate that the rubber-modified thermoplastic resin produced in this example is superior. was coagulated with sulfuric acid by a conventional method, and the obtained wet polymer powder was washed, dehydrated, and dried to obtain a dry graft rubber polymer powder. This graft rubber polymer, the acrylonitrile-styrene copolymer produced in Example 1, and the same amount of additives as used in Example 1 were mixed and processed into a pellet using a screw extruder. The composition of the pellet obtained at this time was the same as that of the pellet obtained in Example 1, but there were many pimples on its surface, and its commercial value was not recognized.

Furthermore, the obtained pellets were injection molded and subjected to the same tests as in Example 1 to obtain the evaluation results shown in Table 18.

Table 18 [Effects of the Invention] Comparing the effects of the method of the present invention with the conventional method, the first advantage in terms of process is that there is no need to powderize the polymer. More specifically, (1) dehydration after coagulating latex to obtain wet powder;
Processes such as drying, air transportation of powder, and storage can be omitted, and processing can be simplified.

(2) Heat loss in the dryer can be avoided.

etc., the cost reduction effect is significant. Furthermore, (3) no dust is generated and the work environment is not contaminated.

There are also other effects.

In comparison with the conventional method in terms of quality, (4) in the present invention, the graft rubber polymer particles are dispersed in the thermoplastic resin in the presence of an organic agent, so the graft rubber polymer particles do not stick to each other; Since the graft rubber polymer can be homogeneously dispersed, it is possible to produce a rubber-modified thermoplastic resin of higher quality than before.

(5) In particular, it is possible to produce rubber-modified thermoplastic resins with less appearance defects such as fish eyes.

There is an effect.

Furthermore, in the present invention, by analyzing in detail the addition time and usage effects of the thermoplastic resin, (6) the amount of organic chemicals used can be reduced.

(7) The volume usage efficiency of the device can be improved.

This effect also occurs.

Furthermore, in the present invention, we have investigated in detail the process by which a polymer latex is separated into an organic phase and an aqueous phase and then mixed with a thermoplastic resin to produce a rubber-modified thermoplastic resin. The machine replaced the conventional steps of coagulation, dehydration, drying, bundling, and melt extrusion, and succeeded in greatly simplifying the process.

Thus, the present invention provides a technique for producing high quality rubber-modified thermoplastic resins at low cost.

[Brief explanation of the drawing]

Figure 1 shows the continuous kneading machine used in the present invention, and Figure 2 shows the axial direction of the barrel that is equipped with all the supply ports, drain ports, vents, and discharge ports that may be provided in the extruder used in the present invention. 5 is a cross-sectional view of the barrel of the continuous kneading machine used in the embodiment of the present invention (however, the bearing on the discharge side is omitted), and FIG. Fig. 5 is an axial cross-sectional view of the barrel of the extruder used in the example, and Figure 5 shows the drain port (front view of VD) of the continuous kneader used in the example.
Figure 6 is an x-x' cross-sectional view of Figure 5, Figure 7 is a cross-sectional view perpendicular to the barrel axis of the feed port of the continuous kneader and extruder used in the practical row, and Figure 8 is used in the example. Supply port (II) of the continuous kneader, (cross-sectional view perpendicular to the barrel axis of 110, No. 9
The figure is a plan view of the ventro of the extruder used in the example.
The figure is a sectional view taken along the line X-X' in FIG. 9, and FIG. 11 is a sectional view perpendicular to the barrel axis of the extrusion-like supply port (X) used in the example.
Fig. 12 is a cross-sectional view perpendicular to the axial direction of the discharge port of the continuous kneading machine, and Fig. 13 is a cross-sectional view of the barrel of the continuous kneading machine of other rows used in other examples (however, the discharge port ), Fig. 14 is an axial cross-sectional view of the barrel of the extruder in the other row used in the other examples, and Fig. 13 is a cross-sectional view of the screw element used in the example. Front view of an example, 1st
Fig. 6 is a side view, Fig. 17 is a front view of an example of the kneading disk, Fig. 18 is a side view thereof, Fig. 19 is a front view of another example of the drain port, and Fig. 20 is a front view of an example of the kneading disk. X −X'
FIG. 21 is a front view of another example of the screw element, and FIG. 22 is a side view thereof. In Figures 1 to 22, 1 is the barrel, 21'j is the outer surface of the barrel, 3 is the inner hole of the barrel, 4 is the part, 5 is the opening) 6 is the hole\
7 is a supply port, 8 is a lid, 9 is a ventilation hole, 10 is an opening, 11
is the discharge port, 12 is the flight top of the screw, 13 is the groove of the screw, 14 is the hole through which the screw passes, 15 is the top of the kneading disk, 16 is the slit, 17 is the seal plate of the continuous kneader, 18 is the sliding bearing. 19 is the gland packing attachment part, 20 is the sliding bearing surface, (I) is the supply port for the thermoplastic resin (2), (
II) i Latex (A) supply port, ■) Water-soluble drug (C) supply port, (y) ta Organic drug ■) supply port, (
■ is the supply port for thermoplastic resin (2), (6) is the drain port, (
4) is the supply port for the thermoplastic resin (2), Hat is the supply port for the thermoplastic resin (3), Sono is the discharge port for the organic phase, oo is the supply port for the z organic phase mixture, (X1) C is the thermoplastic resin (2) supply port, (Xll'li thermoplastic resin (3) supply port, (X
III) Nihentro, (XIv) thermoplastic resin (3)
The supply port is shown in (xv), the vent hole is shown in (xv), and the discharge port in (XM)i is shown, respectively. Patent Applicant: Mitsubishi Rayon Co., Ltd. Representative Patent Attorney: Satoshi Sawa Lost Land Map 5
tail,. X Tail 7z Tail a Leap 9 Diagram Qin lOz No. 15 Concave 4 Shi, Lo Figure/3 Bon 77 Figure Fu/6 Concave Figure 79-X ■ L21 Figure/':3 Pit 20 Diagram Tail 22 Procedure Amendment 1. Indication of the case Japanese Patent Application No. 62-282868 Z Name of the invention Relationship to the case of Person who amends the manufacturing method of rubber-modified thermoplastic resin 5 Patent applicant No. 3-19 Kyobashi 2-chome, Chuo-ku, Tokyo (603) Director of Mitsubishi Rayon Co., Ltd. Corporate Philosophy Yatabe Nagai 4, Agent Address: 2-3-19 Kyobashi, Chuo-ku, Tokyo 104
Contents of the 12 Amendments (1) "Alpha-methylstyrene" written in lines 14-15 on page 23 of the specification is amended to "α-methylstyrene." (2) "Polyethylene terephthalate" written on page 24, lines 8-9 of the specification is corrected to "polyethylene terephthalate." (3) “As shown” on page 50, line 16 of the specification
Correct it to "as shown". (4) "Putsu" written on page 54, line 8 of the specification is corrected to "fish eye". \

Claims (1)

[Claims] 1. A graft rubber polymer (1) obtained by emulsion graft polymerization of a vinyl monomer to rubber latex, a thermoplastic resin (
3) and optionally thermoplastic resin (2) when producing a rubber-modified thermoplastic resin using a continuous kneader and an extruder, the following (II), (III), (IV), (VI) and ( (II): latex (A) of graft rubber polymer (1);
(III): A supply port for a water-soluble drug (C) that can coagulate latex (A) in an amount of 10% by weight or less based on the graft rubber polymer (1), (IV): A supply port ( II) and the supply port (B) for the following organic drug (B), which is located on the discharge side from the supply port (III) by a distance (L1) of 1 to 5 times the screw diameter (D), Organic drug (B): Graft It has the ability to dissolve 10 to 600% by weight of the thermoplastic resin (2) based on the total amount of the rubber polymer and the thermoplastic resin (2), and its solubility in water is as low as the drain port described below. Organic agent (VI) that is 5% by weight or less at barrel temperature (E) of (VI): Located on the discharge side from the supply port (IV) by a distance (L2) of 4 times or more and 20 times or less of the screw diameter (D). and a drain port for discharging the aqueous phase separated from the mixture of substances added up to the supply port (V); (IX): discharge port for the organic phase containing the grafted rubber polymer; ), one of the following supply ports (I), (V), and (VIII) must be provided for the thermoplastic resin (2), and (I): Supply port (II) and Supply port for thermoplastic resin (2) located on the drive side from the supply port (III), (V): Supply port for thermoplastic resin (2) located on the discharge side from the supply port (II) and the supply port (III) Port, (VII): If it has a supply port (VIII), it should be located on the drive side from the supply row by a distance (L3) of 2 times or more and 10 times or less of the screw diameter (D), and the supply port (VIII) If not, there is a continuous supply port for the thermoplastic resin (2) located on the drive side by a distance L3 from the discharge port (IX), and, if desired, a supply port for the thermoplastic resin (3) described in (VIII) below. (VIII): 1 of the screw diameter (D) from the discharge port (IX)
It has a supply port for the thermoplastic resin (3) located on the drive side by a distance (L4) that is between twice and 10 times, and the following supply ports, vent ports, and discharge ports (X), (XIII), and (XVI). (X): supply port for supplying the organic phase mixture containing the graft rubber polymer (1) discharged from the continuous kneading machine; (XIII): organic agent (B) and discharged from the drain port (VI); (XVI): Discharge ports for molten rubber-modified thermoplastic resin, and further, if desired, when using thermoplastic resin (2); has the following supply port (X I ), (X1): If it has the supply port (XII), the supply port (
XII) is located on the drive side by a distance (L3) of 2 times or more and 10 times or less of the screw diameter (D), and if it does not have a supply port (XII), it is located on the drive side by a distance L3 from the vent port (XIII). Thermoplastic resin (2) supply port located at , and when thermoplastic resin (3) is used as desired, the following (XII) and (XIV) supply ports are provided, (XII):
At least 1 times the screw diameter (D) from the vent port (G)1
a supply port for thermoplastic resin (3) located on the drive side by a distance (L4) equal to or less than 0 times; (XIV): a supply port for thermoplastic resin (3) located on the discharge side from the vent port (XIII); If the extruder has a supply port (XIV), use an extruder with a vent port (XV) as shown below, if desired. a supply port (VIII) in the continuous kneading machine as a supply port for the thermoplastic resin (3), at least one vent port and no more than two vent ports for removing volatile components contained in the barrel rubber-modified thermoplastic resin; (XII) or (
At least four of the following are established:
The latex (A) is supplied from the supply port (II) of the continuous kneading machine, the water-soluble drug (C) is supplied from the supply port (III), and the latex (A) and the water-soluble drug (C) are separated by a distance L1. Supplying the organic agent (B) from the supply port (IV) to the mixture containing the coagulated latex (A) obtained by mixing in the section,
By kneading in the section of distance L2, latex (A
) is separated into a mixture containing the graft rubber polymer (1) and an aqueous phase, the aqueous phase is discharged from the continuous kneading machine through the drain port (VI), and then the mixture containing the graft rubber polymer (1) is separated. The discharged material is discharged from the discharge port (IX), and then the discharged material is supplied to the extruder from the supply port (X), and then the organic phase mixture containing the graft rubber polymer (1) is heated, and then the organic phase mixture containing the graft rubber polymer (1) is heated. X
III) from the organic agent (B) and the moisture that has not been discharged from the discharge port (VI), and if desired, the thermoplastic resin (2) is added to the continuous kneading machine at the supply port (I) or the supply port ( V) or the supply port (VIII) or the supply port (IX) of the extruder, and mix with the mixture containing the graft rubber polymer (1) and the organic drug (B) in a distance L3. , and the thermoplastic resin (3) is supplied from at least one supply port of the continuous kneading machine supply port (VIII), the supply port (XII) or the supply port (XIV) of the extruder, and the graft rubber polymer is Mixture containing (1) and distance L4
1. A method for producing a rubber-modified thermoplastic resin, which comprises mixing in a section of 1, and degassing volatile components at a vent port (XV) if desired. 2. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is not supplied. 3. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from the supply port (I). 4. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from a supply port (V). 5. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from the supply port (VII). 6. The method for producing a rubber-modified thermoplastic resin according to claim 1, characterized in that the thermoplastic resin (2) is supplied from the supply port (X I ). 7. The method for producing a rubber-modified thermoplastic resin according to any one of claims 1 to 5, characterized in that the thermoplastic resin (3) is entirely supplied from the supply port (VIII). 8. The method for producing a rubber-modified thermoplastic resin according to any one of claims 1 to 6, characterized in that the thermoplastic resin (3) is supplied entirely from the supply port (XII). 9. The method for producing a rubber-modified thermoplastic resin according to any one of claims 1 to 6, characterized in that the thermoplastic resin (3) is supplied from the total supply (XIV). 10. A part of the thermoplastic resin (3) is supplied from the supply port (VIII), and the remainder is supplied from the supply port (XII), according to any one of claims 1 to 5. A method for producing rubber-modified thermoplastic resin. 11. A part of the thermoplastic resin (3) is supplied from the supply port (VIII), and the remaining part is supplied from the supply port (XIV), according to any one of claims 1 to 5. A method for producing rubber-modified thermoplastic resin. 12. A part of the thermoplastic resin (3) is supplied from the supply port (XII), and the remainder is supplied from the supply port (XIV), according to any one of claims 1 to 6. A method for producing rubber-modified thermoplastic resin. 13. Claims 1 to 12, characterized in that a part of the organic drug (B) is degassed and removed from the vent port (XIII), and the remainder is degassed and removed from the vent port (XV). A method for producing a rubber-modified thermoplastic resin according to any one of the above. 14. In the continuous kneading machine, a compression section is provided between the drain port (VI) and the supply port or discharge port adjacent to the discharge side, and the organic phase containing the graft rubber polymer (1) and the organic agent (B) is compressed. Claims 1 to 1, characterized in that the water that has been dehydrated and compressed and dehydrated is discharged from the outlet (VI).
A method for producing a rubber-modified thermoplastic resin according to any one of Item 3.